EP1485350A1

EP1485350A1 - Use of unsaturated ketones as a perfume

Info

Publication number: EP1485350A1
Application number: EP03744331A
Authority: EP
Inventors: Thomas Markert; Volker Porrmann; Frank Rittler
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2002-03-19
Filing date: 2003-02-17
Publication date: 2004-12-15
Anticipated expiration: 2023-02-17
Also published as: US7582600B2; US20050119158A1; JP4346448B2; ES2426001T3; EP1485350B1; JP2005520875A; WO2003078391A1; DE10212026A1; US20090054299A1

Abstract

Unsaturated ketones of general formula (I) where the groups R1, R2, R3, R4 and R5 independently = H or 1-6 C alkyl groups, which can be saturated or unsaturated, straight-chained, branched or cyclic are characterised by an interesting and original odour characteristic with good emanation and are suitable for use as perfumes, for example in cosmetic preparations, technical products or alcoholic perfumery.

Description

"Use of unsaturated ketones as fragrances"

Field of the Invention

The present invention relates to the use of unsaturated ketones of special structure as fragrances.

State of the art

Many natural fragrances are available in a completely insufficient amount, measured according to need. For example, 5000 kg of rose petals are required to obtain 1 kg of rose oil. The consequences are a very limited world annual production and a high price. It is therefore clear that the fragrance industry has a constant need for new fragrances with interesting fragrance notes. On the one hand, the range of naturally available fragrances can be supplemented, on the other hand it is possible to make the necessary adjustments to changing fashionable tastes. It also makes it possible to meet the ever-increasing need for odor improvers for everyday products such as cosmetics and cleaning agents.

In addition, there is generally a constant need for synthetic fragrances that can be manufactured cheaply and with consistently high quality and that have original olfactory properties. In particular, they should have pleasant, near-natural and qualitatively novel odor profiles of sufficient intensity and should be able to influence the scent of cosmetic and consumer goods in an advantageous manner. In other words, there is a constant need for compounds that have characteristic new odor profiles with high adhesive strength, odor intensity and radiance. Watanabe, Shoji; Fujita, Tsutomu; Suga, Kyoichi; Yokoyama, Toshiro describe in J. Appl. Chem. Biotechnol. 1975, 25, 733-736 the production of, inter alia, a compound which is referred to as "1- (4-methyl-cyclohex-3-en-1-yl) -l-oxo-4-pentene". It is immediately and unambiguously apparent to the person skilled in the art that this substance, which is numbered as compound (IV), is incorrectly designated and the structural formula is incorrectly reproduced. As can be seen from the manufacturing instructions disclosed on page 735 - in accordance with the rest of the publication - it is that the compound (III) was reacted with vinyl magnesium chloride. As is immediately apparent to the person skilled in the art, vinyl groups are “transferred” to (III) so that the resulting compound (IV) must have a formula in which the side chain is shorter by one CH ₂ group. This is also in accordance with the fact that the additional compound (V), which apparently resulted from further reaction of the primary product with vinyl magnesium chloride, also carries vinyl groups. Compound (IV) must therefore have the designation 1- (4-methyl-cyclohex-3-en-1-y 1) -1-oxo-3-butene.

Nothing is disclosed about the olfactory properties or the suitability of the compounds as fragrances.

Description of the invention

It has been found that the compounds of the general formula (I) meet the above requirements excellently in every respect and can be used advantageously as fragrances with different nuanced odor notes with good adhesive strength.

The present invention firstly relates to the use of unsaturated ketones of the general structure (I)

(I) in which the radicals R _h R ₂ , R ₃ , R and R ₅ independently of one another denote hydrogen or alkyl groups having 1 to 6 carbon atoms, which may be saturated or unsaturated, straight-chain or branched or cyclic, as odoriferous substances.

In the context of the present invention, the following chemical individuals of the formula (I) are particularly preferred:

1 - (4-methyl-cyclohex-3 -en- 1 -yl) -4-penten-1 -one (I-a)

3,3-dimethyl-1 - (4-methylcyclohex-3-enyl) -pent-4-en-1 -one (I-b)

1 - (4-methyl-cyclohex-3-enyl) -3-propyl-pent-4-ene-1-one (I-c)

In the use according to the invention, the compounds (I) and in particular the compounds (I-a), (I-b) and (I-c) can be used individually or in a mixture with one another. The use of (I-a) is particularly preferred. In another embodiment, mixtures of the compounds (I) are used.

In a further embodiment, the invention relates to fragrance concentrates consisting of one or more of the compounds of the general structure (I) specified above.

The compounds (I) according to the invention are distinguished by an odor characteristic in which fruity-herbaceous notes dominate. They have excellent stability in cosmetic and consumer perfume formulas. The compounds (I) can be prepared per se by known synthetic methods of organic chemistry. Particularly suitable options for the preparation of the compounds (I) can be found in the example section.

Another object of the invention is a process for the preparation of compounds of the above general formula (I):

Here, l-acetyl-4-methyl-cyclo-3-hexene or l- (l, l-diethoxyethyl) -4-methylcyclohex-3-ene are reacted with olefinically unsaturated alkenols in the presence of an acidic catalyst, the OH group the alkenols are in the alpha position to the C * = C double bond of the alkenol. The OH group of the alkanols is preferably primary, but can also be secondary or tertiary.

In perfume compositions, the compounds (I) enhance the harmony and charisma as well as the naturalness and also the adhesion, the dosage being matched to the desired fragrance note, taking into account the other constituents of the composition.

The fact that the compounds (I) have the above-mentioned fragrance notes was not predictable and is thus further confirmation of the general experience that the olfactory properties of known fragrances do not allow any conclusive conclusions to be drawn about the properties of structurally related compounds, because neither the mechanism of fragrance perception nor that The influence of the chemical structure on fragrance perception has been sufficiently researched and therefore it cannot normally be predicted whether a change in the structure of known fragrances will change the olfactory properties and whether these changes will be judged positively or negatively by the person skilled in the art. The compounds of formula (I) are particularly suitable for modifying and enhancing known compositions due to their olfactory profile. In particular, their extraordinary smell strength should be emphasized, which generally contributes to the refinement of the composition.

The compounds of the formula (I) can be combined with numerous known fragrance ingredients, for example other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts. The range of natural fragrances can include both volatile, medium and low volatile components. The range of synthetic fragrances can include representatives from practically all classes of substances.

Examples of suitable substances with which the compounds (I) can be combined are in particular:

(a) Natural products such as tree moss absolute, basil oil, agricultural oils such as bergotte oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil, cedarwood oil, sandalwood oil, East Indian oil, guaiac oil Cabreuva,

(b) alcohols such as farnesol, geraniol, citronellol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamon alcohol, sandalore [3-methyl-5- (2.2.3-trimethylcyclopent-3-en-l-yl) pentan-2- ol], Sandela [3-isocamphyl- (5) - cyclohexanol], mugetanol,

(c) aldehydes such as citral, HelionaP% alpha-hexylcinnamaldehyde, hydroxycitronellal,

Lilial ^ - [p-tert-buryl-α-methyldihydrozimtaldehyde], methylnonylacetaldehyde,

(d) ketones such as allylionone, α-ionone, β-ionone, isoraldein, methylionone, nootkatone, calone, α-, ß- and γ-irone, Damascone,

(e) esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, witch- nyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, vetiveryl acetate, cyclohexyl salicylate, isobornyl isobutyrate, evernyl, (f) lactones such as gamma-undecalactone, l-oxaspiro [4.4] nonan-2-one, cyclopentadex-xanolidone, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethylene bromide, ethyl bromide, ga , as well as various other components often used in perfumery such as musk and sandalwood fragrances, indole, p-menthan-8-thiol-3-one, methyleugenol and methyl anthranilate.

Also noteworthy is the way in which the compounds of structure (I) round off and harmonize the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant way.

The usable proportions of the compounds (I) according to the invention or their mixtures in fragrance compositions range from about 1-70% by weight, based on the mixture as a whole. Mixtures of the compounds (I) according to the invention and compositions of this type can be used for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants as well as in alcoholic perfumery (e.g. Eau de Cologne, Eau de toilet, extraits) can be used. There is also an application for perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents. To perfume these various products, the compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.01-2% by weight, based on the entire product. However, these values are not limiting limits, since the experienced perfumer can achieve effects with even lower concentrations or build up new types of complexes with even higher doses. Examples

Example 1:

Preparation of l- (4-methyl-cyclohex-3-en-l-yl-4-penten-l-one

Approach:

1) 176 g (1.2 mol) of 4-acetyl-1-methylcyclohexene (from Aldrich)

2) 50 g sulfuric acid 1% (in absolute ethanol)

3) 214 g (1.44 mol) triethyl orthoformate

4) 139 g (2.4 mol) allyl alcohol

Equipment: 2 L three-necked flask, stirrer, thermometer, nitrogen atmosphere, then autoclave Execution: 4-acetyl-l-methylcyclohexene 1) was placed in the flask and mixed with the sulfuric acid-ethanol mixture 2) at room temperature with stirring and exclusion of moisture in about 0.5 hours. Component 3) was then metered in in about 1 hour. The allyl alcohol (component 4) was added in portions. The mixture thus produced was transferred to a steel autoclave insert and heated to 190 ° C. for 5 hours under 20 bar nitrogen. The GC control showed the starting material to decrease to 2% and the formation of a main product by 31.5%.

Working up: The reaction mixture was washed neutral in a separating funnel, the organic phase was separated off and dried over sodium sulfate. Low boilers were distilled off in a water jet vacuum up to approx. 80 ° C. The residue of about 190 g was distilled on a 30 cm Vigreux column. The main amount of 80 g (bp 50-60 ° C / 0.2 mbar) with a GC purity of 80% was again distilled on a Vigreux column, 50 g of product having a purity of 95.3% being obtained ,

Analysis: The IR spectrum (ATR technique) showed characteristic bands at 915, 1353, 1439, 1638, 1703 cm ^"1 and a CH vibration range from 2836 to 3074 cm ^-1 .

The Η NMR spectrum (in CDC1 ₃ , 400 MHz) showed 1 methyl group (2 singlets) at 1.6 ppm and was overlaid by 1 CH ₂ group (doublets, neighboring atom to the olefinic C atom in the cyclohexene ring on which the Methyl group sits). 3 additional CH ₂ groups (2 in the cyclohexene ring and the double bond in the side chain adjacent) gave two multiplet signals at 1.95 (intensity 4H) and 2.1 ppm (intensity 2 H). The CH ₂ group adjacent to the C * = 0 group gave 2 very strongly split multiplets at 2.25 and 2.35 ppm, which was overlaid by degenerate multiplets of the proton on the other side of the keto group at 2.4 ppm. The 4 olefinic protons gave the following signals: 2 doublets (2H, terminal proto- side chain) at 5.0 ppm, the olefinic proton in the cyclohexane ring gave a weakly split signal at 5/35 ppm and the single olefinic proton in the side chain gave 2 strongly split signals (quintets, 1 H) at 5.65 ppm, superimposed.

Description of smell: In the smell Davana, fruity, green, muguet and in the smell, after 24 hours on the smell strip, weak rhubarb.

Note: That the compound l- (4-methyl-cyclohex-3-en-l-yl) -4-penten-l-one prepared according to Example 1 of the present application is clearly different from that described in J. Appl. Chem. Biotechnol. 1975, 25, 733-736 (see above) and there incorrectly structurally represented connection (IV) is also evident from the different odor characteristics.

Example 2:

Preparation of 3,3-dimethyl-1 - (4-meth.ylcycloh.ex-3 -envD-pent-4-en-1-one

Approach:

1) 65 g (0.3 mol) l- (l, l-diethoxyethyl) -4-methylcyclohex-3-ene

2) 37.9 g (0.44 mol) of 3-methyl-2-buten-l-ol (from Aldrich)

3) 1.7 g acetic acid, conc

4) 1.7 g citric acid (Merck)

Apparatus: 0.5 L agitator with thermometer, reflux condenser and water separator

Execution: Components 1), 2) and 3) were introduced together and stirred at 85 ° C. for 2 hours. After addition of component 4, the mixture was stirred at 85 ° C. for a further 2 hours. It was cooled to 50 ° C. and 2.1 g of sodium methylate solution (30% in methanol) were added.

The mixture was then carefully heated to 175 ° C., stirred for 3 hours and about 20 g of ethanol and 3-methyl-2-buten-l-ol were removed as distillate.

Work-up: After GC control, the residue was taken up in ether, washed neutral and dried over sodium sulfate.

After concentration on a rotary evaporator, 56 g of residue were distilled on a 30 cm packed column. In the main run, 40.8 g of product (bp 76-93 ° C / 0.1 mbar) with a GC purity of 91.9% were isolated.

Analysis: The ¹ H-NMR spectrum (in CDC1 ₃ , 280 MHz) showed 2 methyl groups (2 singlets, geminal methyl groups on C-3) at 1.0 ppm and 1.1 ppm. The methyl group on the cyclohexene ring showed 2 signals (approx. 1.5 Hs each) at 1.55 and 1.65 ppm. The 3 CH ₂ groups in the cyclohexene ring give multiplet signals at 1.5 (approx. 2H) and 1.95 (intensity 4H). The CH2 group adjacent to the C = 0 group gave 2 very differently split signals (singlet and multiplet, 2 Hs) at 2.5 ppm. The proton adjacent to the keto group on the cyclohexene ring appeared as a strongly split multiplet at 2.2 ppm. The olefinic protons gave a ddd at 5.9 ppm (IH), a doublet from the doublet at 5.0 ppm (2Hs) and a broad signal for the olefinic proton in the cyclohexene ring at 5.4 ppm).

Odor characteristics: Green, fruity, greasy, lime in the smell and after smell, fruity, woody, muguet, bergamot after 24 hours on the smell strip.

Example 3:

Preparation of 1 - (4-methyl-cyclohex-3-enyl -3-propyl-pent-4-en-1-one

Approach:

1) 65 g (0.3 mol) l- (l, l-diethoxyethyl) -4-methylcyclohex-3-ene

2) 44 g (0.44 mol) of trans-2-hexen-l-ol (from Fluka)

3) 1.1 g conc. acetic acid

4) 1.1 g of citric acid (Merck)

Apparatus: 0.5 L agitator with thermometer, reflux condenser and water separator.

n Execution: Components 1), 2) and 3) were introduced together and stirred at 85 ° C. for 2 hours. After addition of component 4, the mixture was stirred at 85 ° C. for a further 2 hours. It was cooled to 50 ° C. and 2.1 g of sodium methylate solution (30% in methanol) were added. The mixture was then carefully heated to 175 ° C., stirred for 3 hours, and about 20 g of ethanol and trans-2-hexen-l-ol were removed as distillate.

Work-up: After a GC check, the mixture was taken up in ether and washed neutral. The mixture was then dried over sodium sulfate, filtered and concentrated on a rotary evaporator.

The residue of 68 g was distilled on a 30 cm packed column. 52.4 g of main run (bp. Approx. 65-85 ° C./0.08-0.04 mbar) with a GC purity of 97.2% were obtained.

Yield: approx. 77.8% of theory

Analysis: The 1H NMR spectrum (280 MHz in CDC1 ₃ ) showed almost all signals double or triple. This is interpreted as meaning that in addition to the regioisomers caused by the Diels-Alder reaction, the isomers possible by the Claisen rearrangement are also present:

The methyl group at the end of the side chains gave a signal mountain from superimposed triplets at 0.9 ppm (3Hs). Two multiplets (approx. 4 Hs) were between 1.1 and 1.4 ppm; these are probably assigned to the 2 CH ₂ groups from the side chain. The methyl group a cyclohexene ring gave broad singlets at 1.6 and 1.7 ppm (approx. 1.5 Hs each). At 1.9 and 2.0 ppm there were 2 further signal clusters (approx. 3Hs) which correspond to a CH group and a CH ₂ group which are in the β-position and adjacent to a double bond. At 2.1 and 2.15 ppm there were 2 singlets with one echo each (approx. 4H) and at 2.3-2.7 ppm multiplets and 3 singlet tips (approx. 3 H) from the immediate vicinity of the keto group. The olefinic CH2 gave a multiplet between .4.9 and 5.2 ppm (2Hs) and the neighboring olefinic H a signal group in correlation at 5.6 ppm (IH). The olefinic proton from the cyclohexene ring formed a broad singlet at 5.4 ppm (IH).

Odor characteristics: Green, herbaceous, fresh, citrus, jasmine note in the smell and after smell, after 24 hours on the smell strip: terpene, grapefruit, skin.

Claims

Patent claims

1. Use of unsaturated ketones of the general structure (I)

(I) wherein the radicals R _ls R _2, R _3, R and R ₅ are independently hydrogen or alkyl groups having 1 to 6 carbon atoms, the saturated or unsaturated, straight-chained or branched or may be cyclic, as perfumes.

2. 1 - (4-Methyl-cyclohex-3 -en- 1 -yl) -4-penten-1 -one.

3. 3, 3-dimethyl-1 - (4-methylcyclohex-3-enyl) -pent-4-ene-1 -one.

4. 1 - (4-methyl-cyclohex-3-enyl) -3-propyl-pent-4-ene-1 -one.

5. Fragrance concentrates consisting of one or more of the compounds of the general structure (I)

⁽ 0 in which the radicals RR ₂ , R ₃ , R ₄ and R ₅ independently of one another are hydrogen or alkyl groups having 1 to 6 carbon atoms, which can be saturated or unsaturated, straight-chain or branched or cyclic.

6. Fragrance substance compositions containing one or more compounds (I) general structure (I)

(I) in which the radicals RR ₂ , R ₃ , R and R ₅ independently of one another denote hydrogen or alkyl groups having 1 to 6 carbon atoms, which may be saturated or unsaturated, straight-chain or branched or cyclic, the compounds (I ) in an amount of 1 to 70 wt .-% - based on the entire composition - are included.

7. Process for the preparation of compounds of general structure (I)

(I) in which the radicals R _b R ₂ , R ₃ , _t and R ₅ independently of one another denote hydrogen or alkyl groups having 1 to 6 carbon atoms, which may be saturated or unsaturated, straight-chain or branched or cyclic, characterized in that that 1-acetyl-4-methyl-cyclo-3-hexene or 1 - (1, 1-diethoxyethyl) -4-methylcyclohex-3 - ene in the presence of an acid catalyst with olefinically unsaturated alkenols converts, the OH group of the alkenols being in the alpha position to the C = C double bond of the alkenols.